Lab on the Microneedles: A Wearable Metal-organic Frameworks-Based Sensor for Visual Monitoring of Stress Hormone.

Abnormal secretion and dysrhythmias of cortisol (CORT) are associated with various diseases such as sleep disorders, depression, and chronic fatigue. Wearable devices are a cutting-edge technology for point-of-care detection and dynamic monitoring of CORT with inspiring convenience. Herein, we developed a minimally invasive skin-worn device with the advanced integration of both interstitial fluid (ISF) sampling and target molecule sensing for simultaneous detection of CORT via a microneedle-based sensor with high sensitivity, excellent efficiency, and outstanding reproducibility. In the microneedle patch, swellable hydrogel was employed as the adsorption matrix for ISF extraction. Meanwhile, europium metal-organic frameworks (Eu-MOF) wrapped in the matrix played a vital role in CORT recognition and quantitative analysis. The wearable and label-free Eu-MOF-loaded microneedle patch exhibited high sensitivity in CORT detection with the detection limit reaching 10-9 M and excellent selectivity. Molecular dynamics simulation-driven mechanism exploration revealed that the strong interface interaction promoted fluorescence quenching of Eu-MOF. Moreover, in vitro and in vivo investigation confirmed the feasibility and reliability of the sensing method, and excellent biocompatibility was validated. Overall, a sensitive approach based on the wearable Eu-MOF microneedle (MN) patch was established for the simultaneous detection of CORT via visible fluorescence quenching with exciting clinical-translational ability.

Metal-organic frameworks-based microtrapper for real-time monitoring of targeted analyte and mechanism study.

Interstitial fluid (ISF) provides important information of clinical value and physiological significance beyond blood tests for obtaining more precise health information and disease theranostics. Generally, current strategies are limited to simple extraction with time-consuming follow-up procedures. Facing challenges in efficient and real-time monitoring of target analytes in transdermal ISF, we develop metal-organic framework (MOF)-functionalized microneedle (MN) patches to achieve efficient antibiotics sampling, coupling direct analysis in real time mass spectrometry (DART-MS). The MOF MN microtrapper is constructed in a double-layered structure with a hard core and a better tissue penetration was accomplished. The MOF-based microtrapper manifests good in-vitro and in-vivo antibiotics tracking capability with a semi-quantitative method established. Moreover, the hydrogen-bond driven interaction is clarified by using molecular dynamics simulations (MDS) and related computational analysis. Good penetration safety is confirmed by histological analysis with promising clinical transnationality. We anticipate MOF MN-based microdevices provide a versatile minimally invasive strategy for transdermal ISF extraction and an extendable platform for a range of target molecules monitoring, including drugs, metabolites, biomarkers, et c, with promising clinical transnationality.

Magnetic Zr-Based Metal-Organic Frameworks: A Highly Efficient Au (III) Trapper for Gold Recycling.

In this work, the magnetic Zr-based MOF composites with excellent retrievability were prepared using Fe3O4@SiO2 as the core and UiO-66-NH2 as the shell. Fe3O4@SiO2 core could introduce mesopores and result in capillary condensation in MOF composites, which aggravated with the dosage of Fe3O4@SiO2. The as-synthesized MOF composites could be rapidly retrieved from aqueous solution via magnetic separation in 10 seconds. pH imposed an important effect on Au (III) adsorption by governing the ion exchange and electrostatic interaction between Au (III) anions and adsorbents, and the optimal adsorption happened at pH 7. The adsorption process fitted well with the pseudo-second order kinetics model and Langmuir adsorption model. The maximum adsorption capacity of Au (III) by FSUN-10 and FSUN-50 at 298 K were determined to be 611.18 mg∙g-1 and 463.85 mg∙g-1, respectively. Additionally, Au (III) uptakes increased with temperature. Beyond experiments, the adsorption mechanisms were thoroughly studied through systematic characterization, molecular dynamics simulation (MDS) and density functional theory (DFT) study. It was verified that Au (III) was adsorbed via coordination to hydroxyl and amino groups and was reduced to Au (I) and Au (0) by amino groups. The diffusion coefficient of Au (III) along UiO-66-NH2 was calculated to be 5.8 × 10-5 cm2∙s-1. Moreover, the magnetic Zr-based MOF composites exhibit great industrial value in gold recycling with high adsorption selectivity and good recyclability.

Modification of metal-organic framework composites as trackable carriers with fluorescent and magnetic properties.

A fluorescent metal-organic framework (EuMOF) based on Eu3+ nodes coordinated by 1,1':2',1″-terphenyl-4,4',4″,5'-tetracarboxylate (H4ttca) linkers has been developed as a trackable carrier with inherent fluorescence. Since Fe3O4 nanoparticles (NPs) have great value in versatile applications in vivo/vitro including imaging, cell isolation and magnetic responsivity, Fe3O4 NPs were introduced in the EuMOF composites to enhance the multifunctionalities. It has been demonstrated that the Fe3O4 NPs functionalized EuMOF composites have capability for tumor cell retrieval from matrix followed by anti-cancer drug release, which is promising to be developed as an integrated drug screening platform. Cytotoxicity was evaluated and the EuMOF-based nanocomposite exhibits significantly greater (up to 4x) biocompatibility tested on MCF-7 cells than the Zn-based MOF (the same ligand). Moreover, the EuMOF nanocarrier is capable of loading and releasing anti-cancer drugs in a controllable manner, where Doxorubicin (Dox) functionalized as a payload. Controllable release was successfully achieved after incubation with tumor cells and endocytosis analysis was obtained through the fluorescent imaging which offers monitoring of apoptosis after cargo release. Overall, fluorescent/magnetic properties of EuMOF has been investigated systematically, making it easy to be tracked in potential in vivo/vitro applications. As a drug carrier, it is biocompatible and shows highly efficient drug loading within 5 min, holding great promise in potential therapeutic delivery and other clinical applications.

Selective and efficient adsorption of Au (III) in aqueous solution by Zr-based metal-organic frameworks (MOFs): An unconventional way for gold recycling.

Recycling precious metals from secondary resources is of great environmental and economic significance. In this study, the Zr-based MOFs UiO-66-NH2 was synthesized and used to adsorb Au (III) in aqueous solution. The ultrafine particle size (∼50 nm), excellent crystallinity and huge specific surface area (1039.2 m2 ·g-1) were verified by transmission electron microscope (TEM), powder X-ray diffraction (PXRD) and surface area analysis. About 50 % Au (III) was adsorbed within 6 min and the maximum adsorption capacity at 298 K reached up to 650 mg·g-1, showing superiority to traditional adsorbents. The general order kinetics model and Liu equation were suitable to describe the adsorption process, which was spontaneous, endothermic and driven by the increasing system entropy. Electrostatic attraction between -NH3+ and Au (III) anions and inner complexation to Zr-OH played a vital role in adsorption. Au (Ⅲ) was reduced to Au° by amino groups via redox reaction certified by X-ray photoelectron spectroscopy (XPS), PXRD and high-resolution transmission electron microscopy (HRTEM) analysis. Moreover, UiO-66-NH2 displayed high selectivity, robust stability and excellent reusability, making it an ideal candidate for gold recycling in industrial practice.